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Vapor phase nitration of benzene using mesoporous MoO3/SiO2 solid acid


catalyst
S. B. Umbarkar, A. V. Biradar, S. M. Mathew, S. B. Shelke, K. M. Malshe, P. T. Patil, S. P. Dagde,
S. P. Niphadkar and M. K. Dongare*
Published on 28 March 2006. Downloaded by University of Illinois at Chicago on 27/10/2014 17:10:17.

Received 4th January 2006, Accepted 15th March 2006


First published as an Advance Article on the web 28th March 2006
DOI: 10.1039/b600094k

Nitration of benzene has been carried out in the vapor phase, using dilute nitric acid as the
nitrating agent, over mesoporous MoO3/SiO2 solid acid catalyst with more than 90% benzene
conversion and 99.9% selectivity for mononitrobenzene. A series of MoO3/SiO2 catalysts with
varying MoO3 loadings (1–30 mol%) were prepared using a sol–gel technique and characterized
using X-ray diffraction analysis (XRD), BET specific surface area analysis, temperature-
programmed desorption (TPD) of ammonia, and FTIR spectroscopic analysis of adsorbed
pyridine. XRD analysis revealed the amorphous nature of the catalyst for 1 and 10 mol% MoO3
loading, and the formation of a crystalline a-MoO3 phase on the amorphous silica support at
higher MoO3 loading. The BET surface area for pure silica support was 606 m2 g21 and the pore
size distribution in the range 40–80 Å, showing the mesoporous nature of amorphous silica. The
BET surface area decreased to 583 m2 g21 with incorporation of 1% MoO3 and further decreased
to 180 m2 g21 with increasing MoO3 loading up to 20%. Above 10% MoO3 loading, formation of
crystalline MoO3 clusters on amorphous silica was observed. Ammonia-TPD showed a drastic
increase in acid strength after addition of 1% MoO3 compared to pure silica support and the
acid strength increased with increasing MoO3 content. Among the series of catalysts prepared,
MoO3/SiO2 containing 20 mol% MoO3 was found to be the most active catalyst for benzene
nitration, without showing any deactivation after more than 1000 h, showing a very high potential
for commercialization.

1. Introduction nitrobenzene was low. Kuznetsova et al.3 have studied vapor


phase nitration of benzene using 56% nitric acid over
Nitration of aromatic substrates is a widely studied reaction H-ZSM-5 at 140–170 uC. However, the catalyst was found to
because of its industrial importance. Catalytic hydrogenation get rapidly deactivated (,3 h) due to strong adsorption of
of aromatic nitro-compounds is commercially practiced to reactants and products on the surface as well as in the pores
produce a variety of aromatic amines that have applications of the zeolite, and these species were totally desorbed at only
as chemical intermediates and specialty chemical products. 220–250 uC, as CO, CO2 and NO. Sato et al.4,5 have studied
Many nitro-aromatics are extensively used as intermediates for vapor phase nitration of benzene over different solid acid
the manufacture of dyes, pharmaceuticals, perfumeries and catalysts, such as montmorillonite ion-exchanged with a
pesticides. Nitration of benzene, an industrially important multivalent metal ion, mixed oxides (e.g., TiO2–MoO3), the
reaction, is conventionally carried out in the liquid phase using same oxides treated with sulfuric acid at 500 uC and partially
a mixture of 56–60% (w/w) H2SO4, 27–32% (w/w) HNO3, and neutralized heteropolyacids. Although supported sulfuric
8–17% (w/w) H2O as the nitrating agent at a temperature of acid showed good results for the vapor phase nitration of
50–90 uC.1 A large quantity of dilute sulfuric acid is generated benzene, catalytic activity dropped rapidly after 144 h
because of water formed in the reaction. As dilute sulfuric acid on-stream because of leaching of sulfuric acid.6
cannot be used for nitration, it has to be concentrated for In continuation of our earlier efforts on the use of solid acid
recycling, which is an energy intensive and costly process. The catalysts for nitration of aromatics,7–9 we have investigated
disposal of this large quantity of dilute sulfuric acid poses vapor phase nitration of benzene using molybdenum oxide
environmental problems, making nitration of benzene one of supported on mesoporous silica as a solid acid catalyst and the
the most hazardous industrial processes. Nitration of benzene results are presented in this paper.
without use of sulfuric acid would be an attractive alternative, and
various types of solid acids have been tried with limited success.
Vapor phase nitration of benzene over solid acid catalysts
2. Experimental
has been tried by Suzuki et al.,2 however the yield of 2.1. Catalyst preparation
MoO3/SiO2 catalysts with varying molybdenum oxide molar
Catalysis Division, National Chemical Laboratory, Pune 411008, India.
E-mail: mk.dongare@ncl.res.in; Fax: +91-20-25902633; concentrations (1, 10, 20 and 30 mol%) were prepared by a sol–
Tel: +91-20-25902044 gel technique. Ammonium heptamolybdate (AHM) and ethyl

488 | Green Chem., 2006, 8, 488–493 This journal is ß The Royal Society of Chemistry 2006
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silicate-40 (CAS registry no. 18945-71-7) were used as the


molybdenum and silica sources, respectively.
In a typical procedure, 20 mol% MoO3/SiO2 catalyst was
synthesized by dissolving 14.11 g of AHM in 40 ml of water at
80 uC. This hot solution was added dropwise to a dry isopropyl
alcohol solution of ethyl silicate-40 (48.0 g) with constant
stirring. The resultant transparent greenish gel was air-dried
and calcined at 500 uC in air in a muffle furnace for 12 h.
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Similarly, catalysts with 1, 10 and 30 mol% molybdenum oxide


loading were prepared.
For comparison, pure, high surface area silica catalyst was
prepared by adding 52 g of ethyl silicate-40 to 30 g of dry
isopropyl alcohol; to this mixture 0.02 g of ammonia solution
(25%) was slowly added with constant stirring. The trans-
parent white gel thus obtained was air-dried and calcined in a
muffle furnace at 500 uC for 12 h.
Fig. 1 The XRD patterns of (a) silica and (b) 1, (c) 10, (d) 20 and (e)
2.2. Catalyst characterization 30 mol% MoO3/SiO2.
The X-ray diffraction analysis was carried out using a Rigaku
X-ray diffractometer (Model DMAX IIIVC) with Cu-Ka included (Fig. 1a). The patterns show the amorphous nature of
(1.542 Å) radiation. Temperature programmed desorption of the material at lower Mo loading (Fig. 1b,c). Catalysts with
ammonia (NH3-TPD) was carried out using a Micromeritics 20% Mo loading (Fig. 1d) show crystalline nature with intense
Autocue 2910. BET surface area was determined using NOVA peaks at 2h = 12.9, 23.4, 25.8 and 27.4u corresponding to
1200 Quanta chrome instrument. a-MoO3 in the orthorhombic phase. No b-MoO3 phase is
The acidity of the samples was determined by pyridine observed in the structure because the samples were calcined at
adsorption studies using a Shimadzu 8000 series FTIR 500 uC, a temperature at which the b-MoO3 phase is not
spectrometer arranged for DRIFT technique. stable.10 It is interesting to note that even though the MoO3 is
in the crystalline form at higher Mo loading, the silica support
2.3. Catalytic activity still retains its amorphous nature, leading to the high surface
area of the catalysts.11 In the case of 30 mol% MoO3/SiO2, a
Vapor phase benzene nitration was carried out using a down- very clear crystalline a-MoO3 phase is observed (Fig. 1e).
flow glass reactor with a fixed catalyst bed at atmospheric However, absence of the hump in the 2h range of 20–30u for
pressure. In a typical nitration experiment, 10 g of granulated amorphous silica indicates the formation of bulk molybdenum
catalyst was loaded in a tubular glass reactor of 15 mm oxide, as 30 mol% (y52 wt%) MoO3 is quite high and forms
diameter and 25 cm length. The upper part of the reactor was a mixed oxide phase with amorphous silica. Up to 20 mol%
packed with inert ceramic beads as a preheating zone. The MoO3 loading there is uniform distribution of MoO3 on the
glass reactor was fixed inside the heater and the reaction
silica support, however with still higher loading MoO3
temperature was controlled by a thermocouple inserted in the
becomes the bulk phase.
catalyst bed.
The surface areas of all the catalysts determined using the
Nitric acid (70%) and benzene were introduced into the flow
BET method are given in Table 1. As expected, a very high
reactor using peristaltic pumps with air as a carrier gas. The
surface area of 606 m2 g21 was observed in the case of pure
reaction mixture was condensed at 8 uC and collected in a
silica because of sol–gel synthesis using ethyl silicate-40 as the
receiver. The reaction mixture was extracted with diethyl ether
silica source. Ethyl silicate-40 is a polymeric form (trimeric
followed by neutralization of unreacted nitric acid using
and tetrameric) of tetraethyl orthosilicate monomer, which on
sodium bicarbonate solution. After separation of the organic
controlled hydrolysis yields silica of a very high surface area.12
layer from the aqueous sodium bicarbonate layer, it was dried
On controlled hydrolysis of ethyl silicate-40; the trimeric
using Na2SO4. The organic layer was analyzed using gas
and tetrameric species form the corresponding trimeric and
chromatography (HP 6890, FID detector, column: HP-5, 60 m,
tetrameric silica structures, which restrict the growth of large
0.25 mm ID).
particles. The surface area was found to decrease with
A few runs were also carried out using the formulated
catalyst (20 mol% MoO3/SiO2) in the form of extrudates
Table 1 Surface area and acidity of the MoO3/SiO2 catalysts
(2 mm 6 5 mm) prepared using silica as binder (20 wt%) and
calcined at 550 uC. Surface Pore Average NH3
area/ volume/ pore desorbed/
Catalyst m2 g21 cm3 g21 diameter/Å mmol g21
3. Results and discussion
Silica 606 0.6132 50.49 0.0317
The XRD patterns of 1, 10, 20 and 30 mol% MoO3/SiO2 1% MoO3/SiO2 583 0.5934 40.69 0.1830
catalysts prepared by the sol–gel technique are shown in Fig. 1. 10% MoO3/SiO2 284 0.5656 40.56 0.7056
20% MoO3/SiO2 180 0.2327 51.64 0.9370
For comparison, the XRD pattern of pure silica is also

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increasing MoO3 loading. During the sol–gel synthesis, an


aqueous solution of AHM is added to ethyl silicate-40, which
hydrolyzes ethyl silicate-40. However, control of the rate of
hydrolysis is difficult, because of the use of excess water for
dissolving AHM, which leads to a decrease in the surface area.
The basic pH of the solution, due to the NH3 liberated during
hydrolysis of AHM, also leads to the formation of a product
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with a lower surface area. It is expected that, as MoO3 loading


is increased, crystalline molybdenum oxide clusters are formed
that cover the amorphous silica support, reducing the total
surface area of the catalyst.
The mesoporosity of the catalysts was evident from the
nitrogen adsorption–desorption isotherms of all the catalysts
including silica, which shows the H4 type of hysteresis. The
average pore diameter for all the catalysts is given in Table 1.
Since no template is used during the synthesis of pure silica or
MoO3/SiO2, the pore size distribution does not show any
specific trend. During the preparation of all the catalysts by
the sol–gel method it is difficult to maintain identical process
parameters. The amount of water used varies as the amount of Fig. 3 FTIR spectra of pyridine adsorbed on (a) silica and (b) 1, (c)
water for dissolving AHM varies. Due to ammonia liberated 10 and (d) 20% MoO3/SiO2.
during the hydrolysis of AHM, the pH of the medium is not
constant. Also, due to the changes in the amount of water and 20 mol% MoO3/SiO2, indicating corresponding increases in
the different basicities of the media, the rate of hydrolysis is acid strength as well as in the number of acid sites. The catalyst
not same for all the catalysts. Due to all these factors, there is with 20% Mo loading showed the maximum number of acid
no specific trend observed in average pore diameter and pore sites (NH3 desorbed: 0.937 mmol g21) as well as the highest
volume of the catalysts. However, pore diameters are in the acid strength.
range 40–80 Å, which confirms its mesoporous nature. Pyridine adsorption studies for the determination of the
Ammonia-TPD experiments were carried out to determine nature of acidity reveal the presence of Lewis acidity in all
the acid strength of the catalyst. The results are shown in Fig. 2, catalysts.11 Fig. 3 shows the IR spectra of pyridine adsorbed
and the amount of NH3 desorbed is given in Table 1. The pure on the catalyst surface. The spectrum of pure silica (Fig. 3a)
silica catalyst shows the lowest acidity, with 0.0317 mmol g21 shows the presence of only Lewis acidity (peak at 1450 cm21)
of ammonia desorbed at a comparatively low temperature, with low acidity, and 1% MoO3/SiO2 sample (Fig. 3b) shows
indicating the presence of a few weaker acid sites. Addition an increase in Lewis acidity as well as acid strength. As the
of 1% MoO3 to the silica support by the sol–gel method MoO3 loading is further increased, the samples show the
increases the acidity almost six times (0.183 mmol g21) with presence of both Brønsted (peak at 1540 cm21) as well as
respect to the number of acid sites as well as the acid Lewis acid sites. The generation of Brønsted acidity may be
strength. The temperature for total desorption of ammonia correlated to the formation of polymolybdate Keggin struc-
increased (275 to 400 uC) with increasing MoO3 loading, up to tures.13 The IR spectra of the catalyst in the framework region
shows the presence of peaks at 959 and 914 cm21, which
corresponds to polymolybdate Keggin structures, which are
reported to exhibit Brønsted acidity. At temperatures of about
500 uC transformation of the hexagonal form of molybdenum
trioxide into its orthorhombic form takes place. The oxide
becomes hydrated and subsequently converted into poly-
molybdenic trimers.14,15 Such structural units are expected to
show Brønsted acidity. The ratio of Brønsted to Lewis (B/L)
acidity increases with increasing Mo loading. Though the
Lewis acidity is found to decrease with increasing Mo loading,
the Brønsted acidity observed at higher Mo loading con-
tributes to an overall increase in the total acidity, which is seen
by NH3-TPD. MoO3/SiO2 catalysts prepared by an impreg-
nation technique are reported to show the presence of only
Lewis acid sites without any Brønsted acidity. Ma et al.16 have
prepared a series of MoO3/SiO2 catalysts (1–16 wt%) by an
impregnation method, and the NH3-TPD showed desorption
at much lower temperature (,250 uC), indicating the presence
Fig. 2 NH3-TPD of (a) silica and (b) 1, (c) 10 and (d) 20% of weak acidity. The amount of ammonia desorbed for
MoO3/SiO2. 1% MoO3/SiO2 is reported to be only 0.056 mmol g21, which

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Table 2 Vapor phase nitration of benzene over 20% MoO3/SiO2


catalysta
Time Benzene Nitrobenzene
on-stream/h conversion (%) selectivity (%)

2 61.7 100
4 71.5 99.8b
Scheme 1 Nitration of benzene to mononitrobenzene.
5 90.0 100
7 89.0 100
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increased to 0.102 mmol g21 for 16% MoO3/SiO2. This shows 9 79.0 100
13 92.0 100
that the acidity of impregnation catalysts is significantly lower 30 84.3 100
compared to the catalysts prepared by sol–gel (present work). 34 89.2 100
100 88.3 100
Catalytic activity 300 86.5 100
500 87.7 99.9b
Nitrobenzene is the major product (99.9% selectivity for 700 89.5 100
1000 88.4 100
mononitrobenzene) in the nitration of benzene by nitric acid a
Conditions: benzene : HNO3 = 1 : 0.7; weight hourly space
using MoO3/SiO2 solid acid catalyst as in Scheme 1. velocity = 0.7 h21; 70 wt% HNO3; temp. = 140 uC. b Remaining
The results of the vapor phase nitration of benzene using product was dinitrobenzene.
70% HNO3 over MoO3/SiO2 solid acid catalysts are shown in
Fig. 4. When MoO3 loading was increased from 1 to 10 mol%,
only a marginal increase in benzene conversion from 70 to 74%
was observed. However, a further increase in MoO3 loading
up to 20% led to the maximum benzene conversion of 92%
without change in the nitrobenzene selectivity. Further
increase in the Mo loading to 30 mol% led to a decrease in
the benzene conversion to 36.6%. This shows that 20 mol%
is the optimum Mo loading, which gives highest catalytic
activity. Above 20% loading, MoO3 forms a bulk phase on
the silica surface, which does not increase the benzene
conversion. Benzene conversion was calculated based on the
use of 1 equivalent of nitric acid.
Considering the higher activity of 20% MoO3/SiO2 catalyst,
the catalyst life was tested for almost 1000 h to check the
stability of the catalyst in an acid environment at higher
temperature. The catalyst activity was constant, without
any considerable decrease in either benzene conversion or Fig. 5 XRD pattern of 20% MoO3/SiO2 used at 140 uC for 1000 h.
selectivity for nitrobenzene, showing the stability of the
catalyst for the nitration reaction (Table 2). showed no change in the crystalline nature of the catalyst. The
The XRD pattern of the catalyst (20% MoO3/SiO2) used for chemical composition of the catalyst, verified by EDXS, also
1000 h of benzene nitration at 140 uC is shown in Fig. 5, which showed no change, confirming the stability of the catalyst in
the nitric acid environment at 140 uC.
The maximum catalytic activity of 20% MoO3/SiO2 is
attributed to the higher acidity of the catalyst. The high
catalytic activity of MoO3/SiO2 in benzene nitration can be
attributed to the redox nature of the molybdenum center. The
Mo6+ center acts as an electron acceptor site, which is
responsible for the generation of a nitronium ion by capturing
an electron occupied in the antibonding orbital of the nitrogen
dioxide molecule. The nitronium ion can also be formed on the
Brønsted acid sites.17

2 HNO3 + 2 Mo6+ A 2 NO2+ + H2O + 2 Mo5+

2 HNO3 + Mo5+ A NO2 + O2 + H2O + Mo6+

NO2 + Mo6+ A NO2+ + Mo5+

Fig. 4 Plot of effect of different MoO3 loadings on benzene 2HNO3 zHz ?½H2 NO3 z ?NOz
2 zH2 O
conversion. (Brnsted acid site)

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Fig. 6 Plot for effect of temperature on benzene conversion and Fig. 7 Plot of effect of weight hourly space velocity on benzene
selectivity. Catalyst 20% MoO3/SiO2 (10 g), weight hourly space conversion and selectivity. Catalyst 20% MoO3/SiO2 (10 g), 140 uC,
velocity = 0.7 h21, 70 wt% HNO3, benzene : HNO3 = 1 : 0.7. 70 wt% HNO3, benzene : HNO3 = 1 : 0.7.

Nitration of benzene using dilute nitric acid can also be Table 3 Vapor phase nitration of benzene using formulated catalysta
attributed to the polarisability of the water molecule coordi-
Time on-stream/h Benzene conversion (%) Selectivity (%)
nated to the cation generating the nitronium ion for the
nitration reaction.5 4 71.3 100
18 72.6 100
Influence of temperature 36 70.6 99.8
50 71.8 100
a
The influence of reaction temperature on benzene nitration has Conditions: benzene : HNO3 = 1 : 0.8; weight hourly space
been studied in the range 120–160 uC (Fig. 6). Initially the velocity = 0.6 h21; 70 wt% HNO3; temp. = 150 uC.
conversion increased from 70% to 85% with an increase in the
temperature from 120 to 140 uC, and then decreased to 75%
this catalyst. Use of silica as the binder led to an overall
with a further increase in the temperature to 160 uC. The
decrease in the molybdenum content of the catalyst, leading to
decrease in the conversion at high temperature is due to the
the decrease in the benzene conversion.
thermal decomposition of nitric acid. At higher temperatures
(160 uC), lots of brown fumes were observed, indicating
decomposition of nitric acid, thus less nitric acid was available 4. Conclusion
for the nitration of benzene leading to a decrease in the
Vapor phase nitration of benzene using dilute nitric acid over
benzene conversion. The selectivity for nitrobenzene decreased
20% MoO3/SiO2 showed more than 90% benzene conversion
marginally with increasing temperature due to the formation
and 99.9% selectivity for mononitrobenzene. The catalyst
of dinitrobenzene.
showed high stability for more than 1000 h on-stream. The
formulated catalyst in the form of extrudates also showed
Influence of weight hourly space velocity (WHSV)
similar activity, suggesting its utility on larger scale. Since
The influence of WHSV on nitration of benzene was studied at sulfuric acid has been totally eliminated in this process, the
140 uC over 20% MoO3/SiO2, at nitric acid to benzene molar process is environmentally benign and has high potential for
ratio 0.9 : 1 (Fig. 7). There was no decrease in benzene commercialization.
conversion when the WHSV was increased from 0.2 to 0.9 h21,
however there was slight decrease in the conversion when the References
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